Pyridine carbonyl amides of the benzene series



Patented Apr. 13, 1948 PYRIDINE CARBONYL AMIDES OF THE BENZENE SERIESPeter F. Gross, Woodsto E. I. du Pont de Nem wn, N. J., assignor to ours& Company, Wily mington, DeL, a corporation of Delaware N Drawing.

This invention relates to new compositions of matter and especially topyridine carbonyl amides which contain an arylamine group of the benzeneseries. These compounds are especially suitable for use as amino basesfor the manufacture of azo dyes.

When combined with ice color coupling components to produce azocompounds, the resulting dyes are represented by the general formulaCH4NCONH-Ph--N=NA, wherein C5H4N--' is the residue of pyridine, Ph isthe residue of a phenylene group and A is the residue of an ice colorcoupling component which is devoid of solubilizing groups. The newpyridine carbonyl amides produce novel azo dyes in coupled combinationsof the kind indicated. For example, such dyes wherein the couplingcomponent is an arylide of beta hydroxy naphthoic acid which is devoidof water solubilizing groups are novel blue azo dyes. They have moresatisfactory light fastness, resistance to chlorine and dischargeabilitythan dyes of similar structure which contain furoylor thenoyl-groupsinstead of pyridine carbonyl groups. Similar and other improvements arenoted in other dyes which comprise these diazo components and otherwater insoluble coupling components.

It is among the objects of this invention to provide new pyridinecarbonyl amides which are represented in general by the formula whereinC5H4N- is a pyridine residue and Ph is the residue of a phenylene groupwhich is devoid of water solubilizing groups such as carboxyl andsulfonic acid but which may be substituted by other groups. In thisformula the group may be derived by appropriate means from a phenylenediamine which is devoid of free carboxy and sulfonic acid groups, but.which can be substituted by other groups that do not produce watersolubility. It may also be derived from similar types of nitro-anilines.Another object of the invention is to provide novel amino bases whichare capable of producing improved dyes in shades of blue when coupledwith suitable coupling components. Still other objects of the inventionwill be apparent from the following description.

The objects of the invention may be attained conveniently by reacting apicolinic, nicotinic or iso-nicotinic acid with a 3-nitroor4-nitro-aniline to produce a nitro pyridine carbonyl amino compound. Thenitro group of this compound is then reduced to amino by appropriatemeans.

The invention will be more fully set forth in the following moredetailed description which includes examples that are given asillustrative embodiments of the invention and not as limitationsOriginal application August 30, 1941, Serial N0. 409,002. plicationJanuary 17,

1 Claim. (Cl. 260-295) Divided and this ap- 1942, Serial No. 427,179

2 thereof. Parts are expressed in parts by weight unless otherwisenoted.

EXA PLE 1 I (a) Preparation of 4-picolinylamz'no-2,5-

diethomy-nitro-benzene oughly with hot water and dried. There wasobtained 114 parts of crude product. The crude product was purified byrecrystallization from the "ethyl ether of ethylene glycol, yielding4-picolinylamino-2,5-diethoxy-nitro-benzene which was a bright yellowcrystalline material melting at 172 C. f l

(b) Preparation of 4-picolinylamino-25 diethomy-aniline crystallizingfrom the ethyl ether of ethylene glycol, the crystalline product of4-picolinylamino- 2,5-diethoXy-aniline was a yellow crystalline materialmelting at 113 C. It is represented by the formula i ?O2H5 oo-NH ONH,

002115 EXAMPL 2 Preparation of 4-pz'colz'nylamino-2,5-

dimethomg aniline A mixture of 72.5 parts of sodium picolinate, parts of2,5-dimethoxy-aniline and 400 parts of toluene was treated with 34 partsof phosphorus tri-chloride. The temperature was raised to'the 3 boilingpoint andthemixture refluxed forrli'hours, The toluene was removed bysteam "distillation.

The residue was cooled, the condensation product.

was separated from the water and dissolved in 300 parts of toluene. Thetoluene solution was.

added slowly to 420 parts of nitric acid. The mixture was held at 50-60C. with good agitation during the addition and it w'asthen heated to andheld at 75 C. for 15 to min'utes. The.

toluene was then removed by distillation and the solid product wasfiltered off, washed with-methyl alcohol and dried, giving 136 partsofthenitrocompound.

The nitro compound was placed in an 'autoclave.

pyridine was'heated at 95 "-l00'ctsforz hours and th'npou'red into 600parts 'ofcold'water. After standing overnight, the crystalline product,a

bright yellow material, was filtered and washed :"withwate'r. until theodor of pyridin could no longer be detected, and then dried. A yield of64 .parts of4-nicotinylamino-2,5-diethoxy-nitrobeiizeneIlliavi-nga-melting point of127 C. was,

A mixture of72.5 parts of sodium picoli'nate, '75

parts of cresidine, 400'parts toluene 'an'd 34 parts phosphorustri-chloride'was refluxed for- 3 hours. The toluene was removed by steamdistillation and the residue was filteredand dried, giving 125 parts ofcondensation product. This was dissolved in 300 parts of toluene and thesolution was filtered from a small amount of insoluble impurity. Thesolutionwas then run slowly'into 420 parts'of 15% nitricacid; Vigorousagitation was maintained, and the temperature was held at theboiling'point of;the-miXtui-'e (80"--85? C.) during the addition andthenfor 45 minutes more. Thereafter the toluene was removed by steamdistillation but the material appeared nottobe completely nitrated. Thematerial was separated from the water layer, and "redissolved "in "300parts toluene. This solution wasrun as before at the boil into 310 partsof 20% nitric acid. 'The mixture was cooled, filteredtand dried,fyilding 58 parts of 2-nitro 4emethoxy- 5 picolinylamino toluene whichwas a crystalline product.

(b) Preparationof'z amino-4emethomye5- pz'colz'nylamino-toluene Amixture of 58* parts of Z-nitro I methoxy-S- 'picolinylamino-toluene, 6parts reducednickel EXAMPLE 4 .v

((1,) Preparation of 4-nicotinylamino-2,5- oliethotry'-,mtrobenzeneAmixture of 45.2 parts of:';i-nitro-2,5-diethoxy aniline, 42 partsnicotinyl chloride, and 80 parts obtained.

(b) Preparation of 4-nicotz'rtylamino-2,5- diethoxy-anilme A niixtureoi'1616 parts of 4-nicotinylamino-2,5- diethoxy-nitro-benzene, 150 partsmethyl alcohol and 5 parts of reduced nickel catalyst was placed in aclosed autoclave and heatedat 100 C. under a .pressure of hydrogen of400-500 ,poundsgauge. 'Afte'r 'thej absorption of 'hydrogen. wascomple'ted,

themixtu're was removed from the autoclave and filtered while still hot.Theffiltrate was evaporated to yield the light-colored crystallineprod.-

uct consisting of -4-nicotinylamino-2,5-diethoxyaniline. The product isre'presentedfb'y the formula eczm

tom;

poured into: 300 parts water and-the solidgproduct -was filtered, washedfree fromzpyridine with water,;anddried. -A-:yield of 21.5 parts sofcrude 4,-iso-nicotinyl-amino-2,5-diethoxynitro hen:- zene wasobtained. This was freed "from'contamination .withunreacted4-nitro-2,5=diethoxyaniline by treatment with-nitrous acidsuflicient completely to diazotizethe unreacted amino body, filteringand washing free from di'azo and from acid.

The product is represented by the formula (b) Preparation of4-iso-mcotinyt-ammo- 2;5-diethoxy -'anilm'e- C. undera pressureofhydrogen-of400 500 pounds gauge. 5 After the absorption of hydrogen.was complete, 1 the mixture was filteredhottct remov-e spent catalyst.The filtrate :was evaporated to yildthe .-cry'stalline4-iso-nicotinylamino-s2 5-diethoxy-aniline.

' :EXAMPLE 6 (a) Preparation of 3-"picolinylamirw=nitrobenzene Aimixturer-of "75 ;p'arts .sodiumwpicolinate 69 parts ammitroaniline and1000 parts toluene was heated to "7 0 C. Then342 parts of-.:pliosphorustri-chloride .was added over a period of to and the crude product wasfiltered off from the residue. This product still contained unreactedm-nitraniline, which was removed by treatment of an aqueous slurry ofthe material with hydrochloric acid and sodium nitrite, filtering, andwashing free from acidand diazotized m-nitraniline. The'dried productconsisted of 75 parts of 3-picolinylamino-nitro-benzene having a meltingpointof 167 C.

f (b) Preparation of 3-picolinylamino-aniline A mixture of 60.8 parts of3-picolinylaminonitrobenzene, 300 parts of methyl alcohol and 6 parts ofreduced nickel catalyst was placed in an autoclave and heated at 100. C.under a pressure of hydrogen of 400-500 pounds gauge until theabsorption of hydrogen was completed. The charge was then removed fromthe autoclave and filtered hot to remove the catalyst. The filtrate wasevaporated to dryness, giving a yield of 49 parts of3-picolinylamino-aniline containing 19.7% nitrogen. The theoreticalcontent of nitrogen in 3-picolinylamino-aniline is 19.72%.

Exsmrrs 7 p (a) Preparation lOf. 4-picoZinylamino-3-chloronitrobenzene Amixture of 75 parts of sodium picolinate, 89 parts of2-chloro-4-nitro-aniline and 1000 parts toluene was heated to 70phosphorus tri-chloridewas added over a period of 10-15 minutes. Themixture was then heated to the boiling point. After refluxing fOr 8hours, the toluene was removed by distillation with steam. The residuewas cooled and filtered, and the crude product was dried andrecrystallized from the ethyl ether of ethylene glycol, washedthoroughly and dried. The purified product consisted of 70 parts of4-picolinylamino-3-chloronitro-benzene having a melting'point of 236 C.

(b) Preparation of 4-picolinylamino-3-chloroaniline (a) Preparation ofz-picolznylammo-4-nitrotoluene A mixture of '75 parts of sodiumplcolinate, 63 parts of 4-nitro-2-amino-toluene and 1000 partstoluenewas warmed to 70 C. and 28 parts phos phorus tri-chloride .Wasadded to the mixture over a period of 10-15 minutes. After the mixturehad been heated to the boiling point and refiuxed for 8 hours, thetoluene was distilled out with steam and the residue was cooled,filtered off and dried, giving 89 parts of crude product. This productwas purified by recrystallizing from to- C. and 34.2 parts of luene. Thepurified product consisting of. 2-picolinyl-a;mino-4-nitro-toluenemelted at 182 C.

(1)) Preparation of Z-picolinylamino-4-aminlotoluene A mixture of 46.3parts of 2-picolinyl-amino-4- Intro-toluene, 4- parts nickel catalystand 200 parts methyl alcohol was hydrogenated in a closed autoclave at100 C. under a pressure of hydrogen of 400-500 pounds gauge until thenitro was reduced to amino. The catalyst was removed by filtering thehot solution and the illtrate was evaporated to a volume of about 60parts, coo1ed,-and filtered. The crystalline product consisting of2-picoliny1amino-4-aminotoluene weighed 33.5 parts when dry. Its meltingpoint was 145 C. and it contained 18.25% nitrogen. The theoreticalcontent of nitrogen in C-13H13ON3 is 18.51%.

ExAMeLE 9 (a) Preparation of 2-picolinylamino-5-nitroanisole toluene waswarmed to 70 C. and 34.2 partsof phosphorus tri-chloride was added overa period of 10 to 15 minutes. After heating the mixture to boiling andrefluxing for 8 hours, the toluene was distilled out with steam and theresidue was cooled, filtered and dried, yielding 105 parts of crudeproduct. The crude product was purified byrecrystallizatlon successivelyfrom the ethyl ether of ethylene glycol, toluene, and ethyl alcohol. Thepurified product consisting of 2-pic0- linylamino-5-nitro-anisole meltedat 209 C. and contained 15.00% nitrogen, 56.81% carbon and 4.35%hydrogen. The theoretical content of nitrogen, carbonand hydrogen inC13H1104N3 is C, and 4.07% H.

(b) Preparation of Z-picolinylamz'no-5-aminoanisole A mixture of 20parts of 2-picolinylamino-5- nitro-anisole, 2 parts reduced nickelcatalyst and 200 parts methyl alcohol was placed in a closed autoclaveand heated at under a pressure of hydrogen of 500-600 pounds gauge. Thecatalyst was removed by filtering the hot solution. The filtrate wasevaporated to a volume of about 60 parts and cooled. A crystallineproduct consistingof 8 parts of 2-picolinylamino-5-aminoanisole' andmelting at 134 C. was filtered OE and dried. An additional quantity ofless pure material was recovered from the filtrate.

EXAMPLE 10 A piece of cotton goods, impregnated in the usual manner witha solution of N-(2'-h'ydroxy- 3'-naphthoyl)-aniline, was dried and a dyewas developed thereon by applying a, diazo bath which was prepared asfollows:

One hundred parts of 4-picolinylamino-2,5-diethoxy aniline was stirredinto 300 parts of water When the development of the color was complete,the piece was rinsed, soaped at the .boil,

L coma-Oren. \.N

The fastness of'the dyeing both to light and to chlorine was superior tothat of the dyeing made by coupling diazotized4-furoylamino-2,5-.diethoxy-aniline with N- (2' -h'y.droxy-3'-'naphthoyl) -aniline on cotton and its fastness to. chlorine was verymuch superior to that of the dyeing made by coupling4-alpha-thenoyl-amino-2,5- diethoxy-aniline withN-(2-hydroxy-3-naphthoyl) -aniline on cotton.

Similar blue 'dyeings having the superior properties of the dyeing ofExample 10 are made in similar manner by using 4-.iso-nicotinylamino-2,5-diethoxy-aniline in the procedure of Example 10 instead of4-picolinylamino 2.5-diethoxy-aniline. N- (2-hydroxy-3 -naphthoy1)-o-toluidine,

the corresponding B-nitro-aniline, the corresponding l-amino-naphthalene and the corresponding p-amino-anisole when used in. suchcombinations as the coupling components of the described dyesgaveidyeings which. had superior propertiesas compared'with similarfuroyland thenoyl containing compounds.

The compounds of the present invention are represented in general by theformula wherein X is from a .group consisting of hydrogen, alkyl having1 to 3carbons, the corresponding alkoxy groups, phenyl, phenoxy, chlorpand bromo; n is not greater than? and the group CtH4NCO- is the residueof a 2'-, 3- or 4- pyridine carboxylic acid.

As illustrative of other primary arylamines of thepyridine-carbonyl-amino compounds ofthe benzene series which can be usedas amino bases to produce azo combinations having properties similar tothose described are mentioned B-brtomo- 8 ene,3-hromo-:4-1-nitroanilme,jzeaminoefienitroediiphenylether, .4'-nitro-2,5-.diiso-:propoxy aniline. .2I-znitro-.4-.amino-'5-nepropoxytoluene, .Z-nitme'i- .aminoeethylbenzene, 2-.amino-5-.nitro-1,4exylene,:5 '2 amino-4 lsopropyle5 nitro=anisole, 2-chloro-3- "nitro-fi-raminotoluene. Any. of the resulting nitro fpyridine carbonyl amino compounds.of. the benzeneseries .may be readily. reduced tothe analogousprimaryamines by suitable reduction ..1'() methods, such as thosedescribed .in the raregoingmxampless .In.:the reductions with nickelcatalyst,v anynickeli hydrogenation catalystcan be used. The temperatureand pressure .of hydrogenation may be considerably varied, Temperaturesof about 50 to about 200 C. and pressures of about 200 .to about 1000pounds-gaugeare suitable. More or less inert solvent can beused besides.the proportions enumerated and any inert solvent besidestoluene ormethyl alcohol can' be used. Byinert organic solventis meant anyorganicsolvent in which the nitrosubstitutedcompound to be treated is solubietoan appreciable extent, which does not'hydrogenate .in the conditionsused to reduce-the nitrogroup and which does not react :with thefinaliproduct except as a solvent. Calciumnarbonate .is not an essentialconstituent of the reduction medium. v

The preferred class of arylamines are pyridinecarbonyl-amides oftheformula .and' especially those whereinlR is from the group consistingof hydrogen, methyl, methoxy, ethoxy and chloro. The dyes made bydiazotizing the amides orthisclass and coupling with: an 'arylide .of2,3-hydroxy-naphthoic acid have the best general properties togetherwith the improvement in dischargeability, chlorine fastness and lightfastn'ess;

This is a division of my copending application Serial'No. 409;002, filedAugust 30, 1941, now Patient .No. 2,365,265.

From the foregoing. disclosure it will be recognized that the inventionis susceptible of modification without departing from the spirit andscope-.thereofand it is to be understood that the invention isnotsrestricted V to the specific illustrations t'hereof herein setforth.

I claim: r v

' Theccompound represented by the formula PETER F. GROSS.

REFERENCES CITED The following references are of record in the file ofthis patent:

V UNITED STATES PATENTS

